Blends of acrylic latexes and derivatives of ester diol alkoxylates

ABSTRACT

Blends of derivatives of esterdiol alkoxylates obtained by reaction thereof with an anhydride, isocyanate or epoxide and an acrylic latex. The blends are useful as coatings.

This application is a division of Ser. No. 837,720, filed Sept. 29,1977.

BACKGROUND OF THE INVENTION

Governmental regulations have placed ever increasing restrictions on theamounts and types of organic volatiles permitted to escape into theatmosphere from coating compositions. Considerable efforts have beenexpended to develop coatings compositions having a minimal amount ofvolatile organic components and this has led to the development ofpowder coatings, radiation-curable coatings, and water-borne coatings.High solids coatings represent another attractive technology to reducesolvent emissions. In these recent developments, the amounts of organicsolvents present are minimal and consequently there is little or noatmospheric pollution.

A compound often used in the production of coating and ink formulationsis 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate (alsoknown as ED-204). However, the normally solid nature of ED-204 and otherester diols has on occasion presented some problems in use. It has beenrecently discovered that ester diols can be reacted with alkylene oxidesto form liquid vehicles which, depending upon the particular alkyleneoxide selected, can be either water soluble or water insoluble; thesehave been called ester diol alkoxylates. Any further discoveries thatwould also serve to lower atmospheric pollution would be of interest foruse in industry.

SUMMARY OF THE INVENTION

It has now been found that certain derivatives of the ester diolalkoxylates can be produced that are useful in the production of coatingand ink formulations. These derivatives are obtained by reacting anester diol alkoxylate with an intramolecular polycarboxylic acidanhydride, or an organic polyisocyanate, or a polyepoxide, orcombinations thereof. The resulting products have been found useful inthe production of high solids compositions. These high solidscompositions additionally contain cross-linkers and can contain pigment,solvents, flow control agent, plus any of the other additivesconventionally present in a coating or ink. They can also be blendedwith other polymers and latexes to yield compositions that produce dryfilms having acceptable properties.

DESCRIPTION OF THE INVENTION

The ester diol alkoxylate derivatives, as well as the ester diolalkoxylates themselves, and the methods for their production arediscussed in detail below.

The Ester Diol Alkoxylates II

The ester diol alkoxylates belong to a new class of materials justrecently discovered and the subject matter of a different application.These ester diol alkoxylates are produced by the reaction of an esterdiol of the structural formula: ##STR1## with an oxirane compound,preferably an alkylene oxide, to produce the ester diol alkoxylate ofthe structural formula: ##STR2## wherein m is an integer having a valueof from 2 to 4, preferably 2 or 3; n is an integer having a value offrom 1 to 5, preferably 1 to 3 and most preferably 1; x and y areintegers each having a value of from 1 to 20, preferably 1 to 10; R isan unsubstituted or substituted, linear or branched alkyl group havingfrom 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms. Thesubstituents on the R group can be any inert group that will notinterfere with the reactions involved and can be, for example, cyano,halogen, alkoxyl, nitro, tertiary amine, sulfo, etc. In the formulas,the variables R, m, n, x and y can be the same or different at thevarious locations.

The novel ester diol alkoxylates (II) are preferably produced by thecatalytic reaction of an ester diol (I) with an alkylene oxide ormixtures of alkylene oxides at an elevated temperature as more fullydiscussed below. One can manufacture the mono, mixed, blocked or cappedadducts.

The alkylene oxides suitable for use in the production of the ester diolalkoxylates are the oxirane compounds such as styrene oxide, ethyleneoxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide,1,3-butylene oxide and 1,4-butylene oxide as well as similar higheraliphatic monoepoxides.

The ester diols of formula I include 2,2-dimethyl-3-hydroxypropyl2,2-dimethyl-3-hydroxypropionate; 2,2-dimethyl-4-hydroxybutyl2,2-dimethyl-3-hydroxypropionate; 2,2-dimethyl-4-hydroxybutyl2,2-dimethyl-4-hydroxybutyrate; 2,2-dipropyl-3-hydroxypropyl2,2-dipropyl-3-hydroxypropionate; 2-ethyl-2 butyl-3-hydroxypropyl2-ethyl-2-butyl-3-hydroxypropionate; 2-ethyl-2-methyl-3-hydroxypropyl2-ethyl-2-methyl-3-hydroxypropionate; and the like.

During the reaction of the ester diol I with the alkylene oxide acatalyst is preferably used in a catalytically effective amount. Theamount of catalyst is from 0.01 to 5 weight percent, preferably from0.05 to 0.5 weight percent, based on the combined weights of ester diolI and alkylene oxide. The catalysts useful are known to those skilled inthe art of alkylene oxide addition chemistry and require little furtherdiscussion here. Illustrative thereof one can mention boron trifluorideetherate, potassium, potassium hydroxide, sodium, sodium hydroxide,Lewis acids, sodium ethoxide, mineral acids, and the like.

The reaction of the ester diol with the alkylene oxide is carried out ata temperature of from 20° to 150° C., preferably from 50° to 120° C. fora period of time sufficient to complete the reaction between thereactants charged. The temperature is often dependent upon theparticular catalyst selected and the alkylene oxide employed. The timewill vary depending upon the size of the batch and the particularreactants and catalysts, and the reaction conditions employed.

The reaction can be conducted at subatmospheric, atmospheric orsuperatmospheric pressure. The pressure is not critical and sufficientpressure is generally used to retain the reactants in the reactor inliquid form.

The amount of alkylene oxide charged to the reaction is from about 2moles to about 40 moles, or more, per mole of ester diol charged;preferably from 2 to 20 moles.

To minimize oxidative side reactions the reaction is preferably carriedout under an inert gas atmosphere using nitrogen, argon or other inertgas.

If desired an inert solvent such as toluene, benzene or1,1,1-trichloroethane can be employed. However, the reaction proceedswell in the absence of any such solvent. In most instances a solvent isnot required as the ester diol is itself a liquid at the elevatedtemperatures employed and serves to maintain a liquid reaction system.

At the conclusion of the reaction the product, consisting of a mixtureof the novel ester diol alkoxylates, is recovered as a residue productand can be used as such; distillation procedures can also be used torecover more refined products.

The ester diol alkoxylates can be used as solvents, vehicles in paint orink formulations, water-borne coatings, as an intermediate in theproduction of other valuable compounds and as a surfactant as well as inproducing the derivatives of this invention.

In a typical embodiment, the ester diol and catalyst are charged to thereactor and the alkylene oxide is then added over a period of time whilemaintaining the desired temperature and pressure. At the completion ofthe addition the contents of the reactor are maintained at the selectedconditions until substantially all of the alkylene oxide has reacted.The product can then be purified, if desired, and recovered byconventional procedures. In some instances one may obtain a productcontaining other glycols as by-products. This can be minimized by properselection of reaction conditions and catalyst.

The Anhydride Modified Ester Diol Alkoxylates III

The catalytic reaction of the ester diol alkoxylates of formula II withan intramolecular polycarboxylic acid anhydride produces a derivativethat contains free carboxyl groups. This can be illustrated by thefollowing formula, in which phthalic anhydride is employed forillustrative purposes, that shows the resultant product ##STR3##obtained by the reaction of two moles of phthalic anhydride per mole ofester diol alkoxylate II.

Illustrative of suitable polycarboxylic acid anhydrides that can be usedone can mention trimellitic anhydride, tetrahydrophthalic anhydride,phthalic anhydride, benzophenone dicarboxylic acid anhydride, succinicanhydride, maleic anhydride, naphthoic anhydride, glutaric anhydride, orany other intramolecular anhydride, including those having substituentsthereon such as halogen atoms, alkyl or alkoxy groups, nitro, carboxyl,aryl, or any other group which will not unduly interfere with thereaction.

The amount of polycarboxylic acid anhydride reacted with the ester diolalkoxylate II can be an amount sufficient to permit reaction with all ofthe hydroxy groups; however, it is preferred to use an amount which isinsufficient to react with all of the hydroxy groups present in theester diol alkoxylate II or derivative thereof. This amount will varyand can be from 0.1 to 1 anhydride equivalent for each hydroxylequivalent or group present in the ester diol alkoxylate II initiallycharged to the reaction mixture and is preferably from 0.1 to 0.6. In amost preferred instance, one anhydride equivalent or anhydride moiety ischarged for each hydroxyl equivalent or group initially present in thereaction mixture. In the reaction a conventional esterification catalystcan be used. These are well known to those skilled in the art.

The ester diol alkoxylate II is reacted with the polycarboxylic acidanhydride at a temperature of from about 75° to 200° C., preferably fromabout 100° to 150° C. The time required for reaction will vary dependingupon the particular reactants charged, the temperature, and the batchsize of the reaction mixture, facts which are well known to thoseskilled in the art. Generally, it has been found that a reaction periodin the laboratory of from 15 to 60 minutes at from 125° to 150° C. isadequate to produce the initial carboxyl-modified addition reactionproduct obtained by the reaction of these two intermediates.

The anhydride modified ester diol alkoxylate III of this reaction is aviscous liquid, in most instances. However, in some instances it hasbeen observed that the product will solidify upon standing at roomtemperature for an extended period of time. This, however, does notdetract from its further utility. Generally, these modified adducts aresoluble in both water and solvents.

The Isocyanate Modified Ester Diol Alkoxylates IV

The catalytic reaction of the ester diol alkoxylates II with apolyisocyanate produces a hydroxyl terminated derivative that containsurethane groups IV. This can be illustrated by the following equation,in which OCNXNCO represents a diisocyanate, and shows the reaction of 2moles of II with one mole of a diisocyanate: ##STR4##

The polyisocyanates that can be used in this invention are well known tothose skilled in the art and should not require detailed descriptionherein. Any of the polyisocyanates can be used alone or in admixturewith other isocyanates including the monoisocyanates. Illustrativethereof one can mention methyl isocyanate, ethyl isocyanate, chloroethylisocyanate, chloropropyl isocyanate, chlorohexyl isocyanate,chlorobutoxypropyl isocyanate, hexylisocyanate, phenyl isocyanate, theo-, m-, and p-chlorophenyl isocyanates, benzyl isocyanate, naphthylisocyanate, o-ethylphenyl isocyanate, the dichlorophenyl isocyanates,butyl isocyanate, n-propyl isocyanate, octadecyl isocyanate,3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane,di(2-isocyanatoethyl)-bicyclo-(2.2.1)-hept-5-ene, 3-dicarboxylate,2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate, tolidinediisocyanate, hexamethylene diisocyanate, dicyclohexyl-4,4'-methanediisocyanate, cyclohexane-1,4-diisocyanate, 1,5-naphthylenediisocyanate, 4,4'-diisocyanato diphenyl ether,2,4,6-triisocyanatotoluene, 4,4',4"-triisocyanato triphenyl methane,diphenylene-4,4-diisocyanate, the polymethylene polyphenylisocyanates aswell as any of the other organic isocyanates known to the averageskilled chemist.

The amount of ester diol alkoxylate II used can be an amount sufficientto permit reaction of the isocyanato group with up to about 0.9equivalent to the total number of hydroxyl groups present. Thus, from0.025 to 0.9 isocyanato equivalent is reacted per hydroxyl equivalent,preferably from 0.04 to 0.5 isocyanato equivalent per hydroxylequivalent, and most preferably from 0.04 to 0.25 isocyanato equivalentper hydroxyl equivalent initially charged. The conventional urethanereaction catalysts are used.

The reaction of ester diol alkoxylate II with isocyanate is conducted ata temperature of from about 25° C. to 100° C. preferably from about 40°C. to 60° C. The time required will vary depending upon the particularreactants charged, catalyst, temperature, and the batch size of thereaction mixture, facts which are well known to those skilled in theart. Generally, it has been found that a reaction period of from 1 to 5hours at from about 40° to 60° C., is adequate to produce theurethane-modified product. This product IV can be used per se or it canbe capped or modified with a carboxylic acid anhydride by the reactionof this hydroxyl terminated isocyanate modified ester diol alkoxylate IVwith an intramolecular carboxylic acid anhydride by the same procedureshereinbefore described for producing the anhydride modified ester diolalkoxylates III. In this instance the compounds produced can berepresented by the general schematic formula: ##STR5## which shows theproduct obtained by the reaction of IV with phthalic anhydride whenfully capped.

The Epoxide Modified Ester Diol Alkoxylates V

The catalytic reaction of the ester diol alkoxylate II with a diepoxidealso produces a hydroxyl terminated derivative. This can be illustratedby the following equation in which two moles of II react with one moleof a diepoxide to produce V: ##STR6## represents a diepoxide.

The diepoxides that can be used in this invention are well known tothose skilled in the art and are fully described in U.S. Pat. Nos.3,027,357; 2,890,194; and 2,890,197. Of particular interest is thatportion of U.S. Pat. No. 3,027,357 beginning at column 4, line 11 tocolumn 7, line 38, which portion and disclosure is specificallyincorporated herein by reference. Among some of the specificillustrative diepoxides disclosed herein one can mention3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, bis(2,3-epoxycyclopentyl) ether, vinyl cyclohexene dioxide,2-(3,4-epoxycyclohexyl)-5,5-spiro-(2,3-epoxycyclohexane)-m-dioxane,bis(3,4-epoxycyclohexylmethyl)adipate, and the like. The cycloalipaticdiepoxides are preferred.

The amount of diepoxide charged to the reaction can vary from about 0.2mole per mole of ester diol alkoxylate II initially charged to thereaction to as high as one mole of diepoxide per mole of ester diolalkoxylate II. Preferably it is from about 0.3 to 0.6 mole of diepoxideper mole of ester diol alkoxylate II initially charged. Conventionalepoxide reaction catalysts are used.

Reaction of the ester diol alkoxylate II with an epoxide is conducted ata temperature of from about 100° C. to 250° C., preferably from about140° C. to 160° C. in the presence of the known conventional catalysts.The time required will vary depending upon the particular reactantscharged, catalyst, temperature, and batch size of the reaction mixture,facts which are well known to those skilled in the art. Generally, ithas been found that a reaction period of from 2 to 10 hours from about140° to 200° C., is adequate to produce the epoxide-modified product.This product can be used per se or it can be capped or modified with acarboxylic acid anhydride by the reaction of this hydroxyl terminatedepoxide modified ester diol alkoxylate V with an intramolecularcarboxylic acid anhydride by the same procedures hereinbefore describedfor producing the anhydride modified ester diol alkoxylates III. In thisinstance the compounds produced can be represented by the generalschematic formula: ##STR7## which shows the product obtained by reactionof V with phthalic anhydride when fully capped.

Formulated Compositions Using Polyols

The modified ester diol alkoxylate derviatives of the types representedby formulas III, IV, IV A, V and V A can be formulated to producecoating and ink compositions by the addition thereto of crosslinkers,polyols, pigments, fillers, and other additives conventionally used inthe production of coatings and inks.

In producing the formulated compositions a crosslinker such as amethylolated melamine can be used in an amount from 25 to 200 weightpercent, preferably from 25 to 100 weight percent, of the modified esterdiol alkoxylate charged. These compounds are well known and many arecommercially available. Those suitable for use can be represented by thegeneral formula: ##STR8## wherein X is hydrogen or --CH₂ OCH₃ andwherein at least two of the X substituents are --CH₂ OCH₃ groups. Thepreferred melamine derivatives are the highly methylolated melamines,with hexamethoxymethylmelamine most preferred. Other amino resins thatcan be used include the urea and benzoguanamine resins.

In addition one can have present a non-volatile low molecular weightpolyol containing from 2 to 6, preferably 2 to 4 hydroxyl groups. Thesenon-volatile low molecular weight polyols can have a molecular weight offrom 62 to about 1000. They can be aliphatic, cycloaliphatic or aromaticin nature. Illustrative thereof one can mentioned ethylene glycol,diethylene glycol, triethylene glycol, propylene gylcol, dipropyleneglycol, neopentyl glycol, butylene glycol, 2,2-dimethyl-3-hydroxypropyl2,2-dimethyl-3-hydroxypropionate, 2,3-dibromo-1,4-but-2-ene diol,bisphenol-A and the ethylene oxide and/or propylene oxide adductsthereof, 2,2-dihydroxymethylpropionic acid, trimethylol ethane,trimethylol propane, pentaerythritol, dipentaerythritol, glycerine,sorbitol, hydrogenated bisphenol-A; 1,1-dihydroxy methane cyclohexane,2,2'-dihydroxymethylbicyclo [2.2.1]heptane, 1,5-pentane diol, decanediol, and the like. Many other non-volatile low molecular weight diolshaving a molecular weight of from 62 to about 1000 are known and can beused; the above enumeration is illustrative only.

Further, one can have present any of the known polycaprolactone polyolsthat are commercially available and that are fully described, forexample in U.S. Pat. No. 3,169,945. As described in this patent thepolycaprolactone polyols are produced by the catalytic polymerization ofan excess of a caprolactone and an organic polyfunctional initiatorhaving at least two reactive hydrogen atoms. The method for producingthe polycaprolactone polyols is of no consequence and the organicfunctional initiators can by any polyhydroxyl compound as is shown inU.S. Pat. No. 3,169,945. Illustrative thereof are the diols such asethylene glycol, diethylene glycol, triethylene glycol, 1,2-propyleneglycol, dipropylene glycol, 1,3-propylene glycol, polyethylene glycol,polypropylene glycol, poly (oxyethylene-oxypropylene) glycols, andsimilar polyalkylene glycols, either blocked, capped or heteric,containing up to about 40 or more alkyleneoxy units in the molecule, 3methyl-1-5-pentanediol, cyclohexanediol, 4,4'methylene-bis-cyclohexanol,4,4'-isopropylidene bis-cyclohexanol, xylenediol,2-(4-hydroxymethylphenyl) ethanol, 1,4-butanediol, and the like; triolssuch as glycerol, trimethylolpropane, 1,2,6-hexanetriol,triethanolamine, triisopropanolamine, and the like; tetrols such aserythritol, pentaerythritol, N,N,N',N'-tetrakis (2-hydroxyethyl)ethylenediamine, and the like.

When the organic functional initiator is reacted with the caprolactone areaction occurs that can be represented in its simplest form by theequation: ##STR9## In this equation the organic functional initiator isthe R"--(OH)_(x) compound and the caprolactone is the ##STR10##compound; this can be caprolactone itself or a substituted caprolactonewherein R' is an alkyl, alkoxy, aryl, cycloalkyl, alkaryl or aralkylgroup having up to twelve carbon atoms and wherein at least six of theR' groups are hydrogen atoms, as shown in U.S. Pat. No. 3,169,945. Thepolycaprolactone polyols that are used are shown by the formula on theright hand side of the equation; they can have an average molecularweight of from 290 to about 6,000. The preferred polycaprolactone polyolcompounds are those having an average molecular weight of from about 290to about 3,000, preferably from about 300 to 1,000. The most preferredare the polycaprolactone diol compounds having an average molecularweight of from 290 to about 500 and the polycaprolactone triol compoundshaving an average molecular weight of from about 300 to about 1,000;these are most preferred because of their low viscosity properties. Inthe formula m is an integer representing the average number of repeatingunits needed to produce the compound having said molecular weights. Thehydroxyl number of the polycaprolactone polyol can be from about 15 to600, preferably from 200 to 500; and the polycaprolactone can have anaverage of from 2 to 6, preferably 2 to 4, hydroxyl groups.

Illustrative of useful polycaprolactones that can be used in theformulated compositions one can mention the reaction products of apolyhydroxyl compound having an average from 2 to 6 hydroxyl groups withcaprolactone. The manner in which these type polycaprolactone polyols isproduced is shown in U.S. Pat. No. 3,169,945 and many such compositionsare commercially available. In the following table there are listedillustrative polycaprolactone polyols. The first column lists theorganic functional initiator that is reacted with the caprolactone andthe average molecular weight of the polycaprolactone polyol is shown inthe second column. Knowing the molecular weights of the initiator and ofthe polycaprolactone polyol one can readily determine the average numberof molecules of caprolactone (CPL Units) that reacted to produce thepolycaprolactone polyol; this figure is shown in the third column.

    ______________________________________                                        TYPE A POLYCAPROLACTONE POLYOLS                                                                    Average  Average No.                                                          MW of    of CPL units                                    Initiator            polyol   in molecules                                    ______________________________________                                         1  Ethylene glycol      290      2                                            2  Ethylene glycol      803      6.5                                          3  Ethylene glycol      2,114    18                                           4  Propylene glycol     874      7                                            5  Octylene glycol      602      4                                            6  Decalene glycol      801      5.5                                          7  Diethylene glycol    527      3.7                                          8  Diethylene glycol    847      6.5                                          9  Diethylene glycol    1,246    10                                          10  Diethylene glycol    1,998    16.6                                        11  Diethylene glycol    3,526    30                                          12  Triethylene glycol   754      5.3                                         13  Polyethylene glycol (MW 200)*                                                                      713      4.5                                         14  Polyethylene glycol (MW 600)*                                                                      1,398    7                                           15  Polyethylene glycol (MW 1500)*                                                                     2,868    12                                          16  1,2-Propylene glycol 646      5                                           17  1,3-Propylene glycol 988      8                                           18  Dipropylene glycol   476      3                                           19  Polypropylene glycol (MW 425)*                                                                     835      3.6                                         20  Polypropylene glycol (MW 1000)*                                                                    1,684    6                                           21  Polypropylene glycol (MW 2000)*                                                                    2,456    4                                           22  Hexylene glycol      916      7                                           23  2-Ethyl-1,3-hexanediol                                                                             602      4                                           24  1,5-Pentanediol      446      3                                           25  1,4-Cyclohexanediol  629      4.5                                         26  1,3-Bis(hydroxyethyl)-benzene                                                                      736      5                                           27  Glycerol             548      4.                                          28  1,2,6-Hexanetriol    476      3                                           29  Trimethylolpropane   590      4                                           30  Trimethylolpropane   750      5.4                                         31  Trimethylolpropane   1,103    8.5                                         32  Triethanolamine      890      6.5                                         33  Erythritol           920      7                                           34  Pentaerythritol      1,219    9.5                                         ______________________________________                                         *Average molecular weight of glycol.                                     

The structures of the compounds in the above tabulation are obvious toone skilled in the art based on the information given. The structure ofcompound No. 7 is: ##STR11## wherein the variable r is an integer thesum of r+r has an average value of 3.7 and the average molecular weightis 527. The structure of compound No. 20 is: ##STR12## wherein the sumof r+r has an average value of 6 and the average molecular weight is1,684. This explanation makes explicit the structural formulas ofcompounds 1 to 34 set forth above.

The concentration of the modified ester diol alkoxylate derivatives ofthe types represented by formulas III, IV, IV A, V and V A in theformulated compositions can be from 20 to 80 weight percent, preferablyfrom 25 to 50 weight percent.

The coating compositions can also contain an organic solvent and acatalyst as optional components. Any of the conventional solvents usedin the coatings industry can be used at a concentration preferably below30 weight percent of the total weight of the coating composition. Whilelarger amounts could conceivably be used, the use of larger amountswould destroy the high solids nature of the coating; solvents aregenerally added in the small amounts indicated to improve flowabilityduring application of the coating composition to the substrate.

In some instance an acid catalyst might be desired to improve theefficiency of the melamine crosslinking reaction during curing. Theconcentration of the catalyst can vary from zero to about 10 weightpercent based on the total weight of the coating composition. Theparticular catalyst used and its concentration are dependent to a degreeupon its catalytic activity and the specific components present in thecoatings composition. These catalysts are known to those skilled in theart and include hydrochloric acid, sulfuric acid, p-toluene sulfonicacid, dodecylbenzene sulfonic acid, phosphoric acid and its alkylderivatives, maleic acid, trimellitic acid, phthalic acid, succinicacid, and the like.

The coatings compositions can also contain pigments, fillers and otheradditives conventionally present in coatings compositions in theirconventional quantities. The particular ones selected are of noconsequence to the basic invention. In preparing the coatingscompositions, the ingredients are mixed by the conventional proceduresused in the production of paints, inks or coatings compositions. Theseprocedures are so well known to those skilled in the art that they donot require further discussion here.

The coatings compositions are applied to a surface or substrate byconventional means and then thermally cured by heating at a temperatureof about 125° to 250° C., preferably from 150° to 200° C. for a periodof time sufficient to obtain a dry film. Generally, this time will rangefrom about one to 30 minutes, preferably from 10 to 20 minutes. Thecomponents present in a particular high solids coating composition willdetermine the temperature and time that will be required to obtain anadequate cure and a good film coating.

The coatings compositions of this invention are high solids coatingscompositions and they can contain as much as 90 weight percent or moresolids therein. Generally the total solids content of the coatingscompositions of this invention range from about 70 to 90 weight percentof the total weight of the coating composition.

Modified Latex Compositions

It has also been found that the modified ester diol alkoxylatederivatives of the types represented by formulas III, IV, IV A, V and VA can be added to latex compositions to improve the properties of thelatexes; in particular acrylic latexes.

The latexes that can be used are known to those skilled in the art andinclude acrylic acid and methacrylic acid derived latexes as well asthose latexes derived from their esters. These latexes are commerciallyavailable and are known to be copolymers of two or more monomers such asmethyl methacrylate, styrene, methyl acrylate, ethyl acrylate, butylacrylate, 2-ethylhexyl acrylate, butyl methacrylate, methacrylic acid,acrylic acid, 2-hydroxyethyl acrylate, vinyl chloride, vinyl acetate,acrylamide, 2-hydroxypropyl acrylate, isobutoxymethyl acrylamide, maleicacid, glycidyl acrylate, vinylidene chloride, vinyl ethyl ether,butadiene, acrylonitrile, diethyl maleate, vinyl ethyl ketone, and thelike. Illustrative of copolymer latexes are vinyl chloride/vinylacetate/methacrylic acid, stryene/ethyl acrylate/methacrylic acid,methyl acrylate/styrene/vinyl acetate/methacrylic acid, and any otherknown latex.

The amount of said modified ester diol alkoxylate derivative that can beadded to the latex can vary from about 5 to about 50 weight percent,based on the total solids content of the latex, preferably from 10 to 20weight percent. It is added to the latex and stirred in by conventionalmeans to obtain uniform distribution therein. The latex formulation canalso contain other components generally present in latex coatingcompositions such as, surfactants, antifoams, bactericides,mildewicides, other coalescing acids, freeze-thaw additives, lightstabilizers, and the like. These are well known to those skilled in theart, as are the amounts thereof required in latex coatings, and do notneed extensive description or discussion herein to enable one skilled inthe art to understand their use.

The latex coating compositions are applied to a substrate by the knownconventional methods. They are cured by heating at a temperature ofabout 125° to 250° C., preferably from 150° to 200° C. for a period oftime sufficient to obtain a dry film. Generally, this time will rangefrom about one to 30 minutes, preferably from 10 to 20 minutes. Thecomponents present in a particular latex coating composition used willdetermine the temperature and time that will be required to obtain anadequate cure and a good film coating.

In the following examples the products were evaluated according to thefollowing procedures.

Crosshatch adhesion refers to a test using 10 parallel, single-edge,razor blades to scribe test films with 2 sets of perpendicular lines ina crosshatch pattern. Ratings are based on the amount of film removedafter applying and subsequently pulling a contact adhesive tape (ScotchBrand 606) away from the surface of a scribed coating at a 90 degreeangle in a fast, rapid movement. It is important to carefully apply andpress the tape to the scribed coating to eliminate air bubbles andprovide a good bond because adhesion is reported as the percent of filmremaining on the substrate with a 100 percent rating indicating completeadhesion of the film in the substrate.

Solvent resistance is a measure of the resistance of the cured film toattack by solvents, usually acetone or methyl ethyl ketone, and isreported in the number of double rubs or cycles of solvent soaked cheesecloth required to remove one-half of a film from the test area. The testis performed by stroking the film with an acetone saturated cheese clothuntil that amount of film coating is removed. The number of cyclesrequired to remove this amount of coating is a measure of the coatingsolvent resistance. Values greater than 100 are reported as 100 whichmeans less than one-half the film was removed after 100 double rubs.

Reverse impact resistance measures the ability of a given film to resistrupture from a falling weight. A Gardner Impact Tester using aneight-pound dart is used to test the films cast and cured on the steelpanel. The dart is raised to a given height in inches and dropped ontothe reverse side of a coated metal panel. The inches times pounds,designated inch-pounds, absorbed by the film without rupturing isrecorded as the reverse impact resistance of the film.

In this application, the following definitions define certain compoundsthat are used in the examples:

Silicone Surfactant I is ##STR13## Epoxide A is3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate.

The following experiments show the production of ester diol alkoxylatesII.

Preparation of Ester Diol Alkoxylates II Experiment A

A reactor was charged with 408 grams of freshly stripped solid2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate and 1.39grams of potassium metal as catalyst and heated to liquify the solid.The reactor was purged with nitrogen and then over a 10 hours additionperiod 528 grams of ethylene oxide were added while maintaining atemperature of from 106° to 114° C. After all of the ethylene oxide hadbeen added, the reaction was continued at 114° C. for 30 minutes tocompletion. The reaction product was neutralized with 1.69 grams ofacetic acid and vacuum stripped at 60° C. and 1 mm of Hg pressure. Theliquid ester diol ethoxylate recovered weighed 922 grams as the residueproduct containing a minor amount of by-products.

The ester diol alkoxylate produced had an average of about six (x+y ofFormula II) ethyleneoxy units in the molecule. The average molecularweight was 480, the Brookfield viscosity was 194 cps. at 26° C. (No. 3spindle, 100 rpm.), the specific gravity was 1.079 g/cc and the Gardnercolor was less than 2. The water dilutability was 250. Waterdilulability defines the grams of water that can be added to 100 gramsof the ester diol alkoxylate to achieve a haze point.

Experiment B

Following the procedure similar to that described in Experiment A, 792grams of ethylene oxide and 612 grams of 2,2-dimethyl-3-hydroxypropyl2,2-dimethyl-3-hydroxypropionate were reacted using 2.1 grams ofpotassium catalyst. The ethylene oxide feed time was about 11 hours.

The liquid ester diol ethoxylate residue product produced weighed 1,391grams; it had an average of about six ethyleneoxy units in the molecule.The average molecular weight was 477, the Brookfield viscosity was 200cps. at 24.5° C. (No. 3 spindle, 100 rpm), the specific gravity was 1.08g/cc and the Pt/Co color was 60. Water dilutability was 296.

Experiment C

Following the procedure similar to that described in Experiment A, 528grams of ethylene oxide and 612 grams of 2,2-dimethyl-3-hydroxypropyl2,2-dimethyl-3-hydroxypropionate were reacted using 1 gram of potassiumas catalyst. The ethylene oxide feed time was about 9 hours.

The liquid esterdiol ethoxylate residue product produced weighed 1,128grams; it has an average of about four ethyleneoxy units in themolecule. The average molecular weight was 392, the Brookfield viscositywas 168 cps. at 27° C. (No. 3 spindle, 100 rpm), the specific gravitywas 1.07 g/cc and the Pt/Co color was 40. Water dilutability was 200.

Experiment D

Following the procedure similar to that described in Experiment A 220grams of ethylene oxide and 510 grams of 2,2-dimethyl-3-hydroxypropyl2,2-dimethyl-3-hydroxypropionate were reacted using 1.1 grams ofpotassium as catalyst. The ethylene oxide feed time was about 5 hours.

The liquid ester diol ethoxylate residue product produced weighed 730grams; it had an average of about two ethyleneoxy units in the molecule.The average molecular weight was 295, the Brookfield viscosity was 285cps at 25° C. (No. 3 spindle, 100 rpm) and the Pt/Co color was 75. Waterdilutability was 86.

Experiment E

A stainless steel autoclave was charged with 3,011 grams of solid2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate and 18grams of boron trifluoride etherate and the contents were heated to 60°C. Then the autoclave was pressured to 10 psi with nitrogen and theethylene oxide feed was started. A total of 2,604 grams of ethyleneoxide was added over a period of about six hours while maintaining thereactor temperature of 65° to 68° C. and the pressure between 10 and 30psi. After all the ethylene oxide had been added the temperature wasmaintained at 65° C. until no ethylene oxide pressure remained in thereactor. The product was cooled to 40° C.; 2 weight percent of magnesiumsilicate neutralizing agent was added and the mixture was stirred at 40°C. for one hour. The temperature was raised to 90° C. and held while avacuum was applied to remove volatile products. This vacuum wascontinued until the pressure in the reactor reached 5 mm. of mercury.The clear/colorless product was pressure filtered to remove insolubles.There was recovered 5,494 grams of the liquid ester diol ethoxylateresidue product having an average of about four ethyleneoxy units in themolecule. The average molecular weight was 382, the Cannon Fenskeviscosity was 90 cks at 100° F. and the Pt/Co color was 30; it had anacid value of 0.06 percent as acetic acid. Gas chromatographic analysisindicated that the product was free of neopentyl glycol and its adducts.

In a similar manner the mixed ester diol ethoxylate/propoxylate isproduced using a mixture of ethylene oxide and propylene oxide as thefeed material. Likewise, the ethoxylate/styroxylate is produced.

Experiment F

Following a procedure similar to that described in Experiment A, 204grams of 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionateand 440 grams of ethylene oxide were reacted at 99° to 115° C. using 1.5grams of boron trifluoride etherate as the catalyst. The ethylene oxidefeed time was about 4.5 hours and the mixture was heated an additional0.75 hours after completion of the addition. Then 13 grams of magnesiumsilicate were added and the mixture was stirred overnight at 50° to 65°C. It was filtered, then stripped at 100° C. for one hour to a pressureof 5 mm. Hg.

The liquid ester diol ethoxylate residue product produced weighed 602.4grams; it had an average of about 10 ethyleneoxy units in the molecule.The Brookfield viscosity was 193 cps at 30° C. (No. 3 spindle, 100 rpm)the specific gravity was 1.046 g/cc and the Gardner color was 1.5. Waterdilutability was 15.6

Experiment G

Following the procedure described in Experiment F, 204 grams of2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate wasreacted with 440 grams of ethylene oxide using 1.5 grams of borontrifluoride etherate as the catalyst. The ethylene oxide addition timewas about 7.5 hours.

The liquid ester diol ethoxylate residue product produced weighed about629 grams after filtering and stripping. It had an average of about 10ethyleneoxy units in the molecule. The Cannon Fenske viscosity at 100°F. was 103.4 cks., the specific viscosity was 1.046 g/cc and the Gardnercolor was 1. Water dilutability was 15.4

Experiment H

Following the procedure described in Experiment F, 125 grams of2,2-dimethyl-3-hydroxypropyl 2-2-dimethyl3-hydroxypropionate was reactedat 48° to 132° C. with a total of 502 grams of ethylene oxide using atotal of 1.3 grams of potassium as the catalyst. The ethylene oxide feedtime was about 9.5 hours. At the completion of the feed 11.9 grams ofmagnesium silicate were added and the mixture was stirred for one hourand then cooled. The ester diol ethoxylate was filtered hot and strippedunder vacuum.

The stripped ester diol ethoxylate residue product recovered weighedabout 585.3 grams. It had an average of about 19 ethyleneoxy units inthe molecule. The Cannon Fenske viscosity was 115.5 cks at 100° F. Onstanding it solidified at 25° C. and melted at about 27° C.

Experiment I

In a manner similar to that described in Experiment A, 805 grams of2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate and 8grams of boron trifluoride etherate were melted at 60° C. in a reactionflask. Over a period of about 1.75 hours a total 811 grams of propyleneoxide were added at a temperature of 57° to 60° C. The reaction mixturewas stirred about another 2 hours; 32.3 grams of magnesium silicate wereadded and stirred at about 70° C. for about 1.5 hours. It was thenstripped at 70° C. for 0.5 hours at 4-5 mm. of mercury and filtered. Theliquid ester diol propoxylate residue product was clear and colorlessand weighed 1,508 grams. It had an average of about 4 propyleneoxy unitsin the molecule.

The following examples serve to further define this invention; parts areby weight unless otherwise indicated.

Preparation of Anhydride Modified Ester Diol Alkoxylates III andFormulations Thereof EXAMPLE 1

Part A--A glass-lined autoclave was charged with 429.47 parts of2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate and 2.4parts of boron trifluoride etherate. The mixture was heated to 55° C.and 370.5 parts of ethylene oxide were added over a period of about 13hours. This mixture was then held at this temperature for four morehours. Then, 2 percent by weight of magnesium silicate was added and thecontents were heated to 90° C. and stirred for 4 hours. Thereafter thepressure was reduced to 20 mm Hg and the product was stripped for fourhours to remove volatiles. Atmospheric pressure was restored withnitrogen, the contents were cooled to 50° C., and transferred to astorage autoclave. Five parts of filter aid were added, the contentswere mixed for 30 minutes, and then filtered and stored. A second batchwas made in the same manner and both batches were blended by placing thematerials in a large autoclave, heating the contents to 90° C., andstripping the product 4 hours at 5 mm Hg. There was obtained a largequantity of the liquid ester diol ethoxylate having an average of about4 ethyleneoxy units in the molecule.

Part B--A 236.7 grams portion of the above liquid ester diol ethoxylate(Part A) was charged to a reactor together with 163.3 grams of phthalicanhydride and 96 grams of 2-ethoxyethyl acetate as the solvent. Themixture was stirred and heated at 140° C. for 30 minutes. The anhydridemodified ester diol ethoxylate III had the following average structuralformula: ##STR14## in which the sum of x and y have an average value ofabout 4. The mixture also contained unreacted ester diol ethoxylate Ithad a Brookfield viscosity of 386 cps at 25° C. and an acid number of124 mgm. KOH/gm.

Part C--A coating composition was prepared by mixing 10 grams of theabove anhydride modified ester diol ethoxylate (Part B), 10 grams ofhexamethoxymethylmelamine, 0.5 gram of N,N-dimethylethanolamine, 3 gramsof distilled water, and 0.05 gram of Silicone Surfactant I. Films wereprepared by casting the above composition on steel pannels with a No. 40wire-wound rod and thermally curing in a circulating air oven. Curingfor 20 minutes at 220° F. afforded no cure. Curing for 20 minutes at250° F. produced films with a 4B pencil hardness, 43 acetone rubs, andgreater than 320 inch-pounds reserve impact resistance. In thiscomposition, cure was achieved even in the absence of catalyst.

EXAMPLE 2

A coating composition was prepared by mixing 10 grams of the anhydridemodified ester diol alkoxylate (Part B) of Example 1, 10 grams ofhexamethoxymethylmelamine as crosslinker, 0.5 gram ofN,N-dimethylethanolamine, 3 grams of distilled water, 0.05 gram ofSilicone Surfactant I, and 0.2 gram of a 40 percent solution ofp-toluenesulfonic acid dissolved in an organic solvent as the catalyst.Cured films were prepared as described in Example 1, Part C. Curing for20 minutes at 220° F. afforded films with 100 acetone rubs, F pencilhardness, and high reverse impact resistance. A film cured at 250° F.for 20 minutes achieved a 2H pencil hardness, 100 acetone rubs, and highreverse impact resistance. The improved properties obtained by the useof a cure catalyst are clearly evident.

EXAMPLE 3

A series of high solids coating compositions was produced by mixing 10grams of the anhydride modified ester diol ethoxylate (Part B) ofExample 1, Epoxide A, stannous octoate catalyst, 0.1 grams of SiliconeSurfactant I, and 1 gram of xylene. Films were prepared from the 86weight percent solids solution as described in Example 1 Part C. Curingat 200° F. for 20 minutes produced clear dry films. The quantities ofreactants used and properties of the cured films are tabulated below;all the films were smooth with high gloss.

    ______________________________________                                                      Experiments                                                                   A     B        C        D                                       ______________________________________                                        Formulation                                                                   Example 1, Part B                                                                            10.0    10.0     10.0   10.0                                   Product, g                                                                    Epoxide A, g   15.0    10.0     7.5    6.0                                    Stannous Octoate, g                                                                          0.23    0.18     0.15   0.14                                   Coating Properties                                                            Reverse Impact 5       250      >320   300                                    in-lbs.                                                                       Acetone Rubs   100     100      92     68                                     Pencil Hardness                                                                              H       2H       2H     2H                                     ______________________________________                                    

Formulation B represents the optimum thermoset characteristics. The Cand D formulations describe the decrease in thermoset characteristicsthat occur when the amount of epoxide is decreased and the resultanthigh impact and hardness that is achieved at the cure conditions used.Formulation A is a hard coating with excellent thermosetcharacteristics.

EXAMPLE 4

A pigmented high solids coating composition was produced by blending 100grams of the anhydride modified ester diol ethoxylate of Example 1, 180grams of titanium dioxide pigment, 3 grams of stannous octoate catalyst,1 gram of Silicone Surfactant I, and 40 grams of xylene in a ball millovernight. Subsequently, 61.73 grams of Epoxide A and 30 grams of xylenewas mixed with 200 grams of the above mixture to afford a 77 weightpercent solids coating composition with a Brookfield viscosity of 180centipoises at 25° C. Films prepared according to the proceduredescribed in Example 1 were cured at 220° F. for 20 minutes. The filmproduced passed 100 acetone rubs, had high gloss, had excellent adhesionand achieved a pencil hardness of 2H.

EXAMPLE 5

Part A--A 360 grams portion of the liquid ester diol ethoxylate of PartA of Example 1 was reacted with 40 grams of phthalic anhydride for 30minutes at 140° C. to produce a phthalic modified ester diol ethoxylatehaving a Brookfield viscosity of 500 cps and an acid number of 40 mgm.KOH/gm.

In a similar manner succinic anhydride can replace phthalic anhydride.

Part B--A coating composition was produced by mixing 100 grams of theabove product of Part A with 100 grams of hexamethoxymethylmelamine, 140grams of titanium dioxide, and 25 grams of 2-ethoxyethyl acetate. Themixture was mixed overnight in a ball mill. Then a 158.5-gram portionwas separated and mixed with 1 gram of phosphoric acid catalyst and 25additional grams of 2-ethoxyethyl acetate. Films prepared by theprocedure described in Example 1 were cured for 20 minutes at 300° F.The film had good solvent resistance (more than 100 acetone rubs), goodadhesion, and 75 inch-pounds reverse impact resistance.

EXAMPLE 6

Part A--A 320 grams portion of the liquid ester diol ethoxylate of PartA of Example 1 was reacted with 80 grams of phthalic anhydride for 30minutes at 140° C. to produce a phthalic modified ester diol ethoxylatehaving a Brookfield viscosity of 1,690 cps and an acid number of 77 mgm.KOH/gm.

Part B--A coating composition was produced by charging 100 grams of theproduct of Part A, 100 grams of hexamethoxymethylmelamine, 140 grams oftitanium dioxide, and 30 grams of 2-ethoxythyl acetate to a ball milland rolling it overnight. Then a 168.5-gram portion of the mixture wasblended with 1.5 grams of phosphoric acid, 0.42 gram of Tinuvin 770® (aUV stabilizer marketed by Ciba-Geigy), 0.11 gram of Irganox 1010® (abranched phenol antioxidant marketed by Ciba-Geigy), 50 grams of2-ethoxyethyl acetate, and 4.55 grams of a polycaprolactone triol havingan average molecular weight of 300 and an average hydroxyl number of560. Films were prepared according to the procedure described in Example1 and cured for 20 minutes at 250° F. The film produced was solventresistant (more than 100 acetone rubs), had a pencil hardness of 2B, andpassed 50 inch-pounds reverse impact resistance.

EXAMPLE 7

Part A--A 280 grams portion of the liquid ester diol ethoxylate of PartA of Example 1 was reacted with 120 grams of phthalic anhydride for 30minutes at 140° C. to produce a phthalic modified ester diol ethoxylatehaving a Brookfield viscosity of 18,280 cps and an acid number of 115mgm. KOH/gm.

Part B--A coating composition was produced by charging 100 grams of theproduct of Part A, 100 grams of hexamethoxymethylmelamine, 140 grams oftitanium dioxide, and 40 grams of 2-ethoxyethyl acetate to a ball milland rolling the mixture overnight. Then a 173 gram portion of themixture was blended with 1.5 grams of phosphoric acid, 40 grams of2-ethoxyethyl acetate, and 4.5 grams of the polycaprolactone triol usedin Example 6, Part B. A film was prepared according to the proceduredescribed in Example 1 and cured for 20 minutes at 250° F. The filmproduced was solvent resistant (more than 100 acetone rubs) and had areverse impact resistance of 200 inch-pounds.

Preparation Of Isocyanate Modified Ester Diol Alkoxylates IV And IV AAnd Formulations Thereof EXAMPLE 8

Part A--A series of isocyanate modified ester diol ethoxylates wasprepared by reacting the ester diol ethoxylate of Part A of Example 1with 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI) at45° C. for about 5 hours. The resulting products contained unreactedester diol ethoxylate and its hydroxyl terminated diurethane dervative.The quantities reacted and properties of the product mixtures producedare tabulated below:

    ______________________________________                                        Run             (1)     (2)     (3)    (4)                                    ______________________________________                                        Example 1, Part A, g,                                                                         95      90      80     85                                     IPDI, g         5       10      20     15                                     Stannous octoate, g                                                                           0.1     0.1     0.1    0.1                                    Product Properties                                                            Brookfield viscosity,                                                                         512     1,588   33,000 6,000                                  cps at 25° C.                                                          Water dilutability, gms.                                                      water/100 gms. product                                                        to haze point.  166     78      21     --                                     ______________________________________                                    

Part B--Aqueous coating compostions were formulated and cured followingthe procedures described in Example 1, Part C. The data are summarizedin the following table:

    __________________________________________________________________________    Coating        1     2     3     4     5     6                                __________________________________________________________________________    Formulation, parts                                                            Example 8, Run (1)                                                                           10    --    --    --    --    --                               Example 8, Run (2)                                                                           --    10    12    8     --    --                               Example 8, Run (3)                                                                           --    --    --    --    10    12                               Example 8, Run (4)                                                                           --    --    --    --    --    --                               Hexamethoxymethylmelamine                                                                    10    10    8     6     10    8                                p-Toluenesulfonic acid                                                                       1.0   1.0   1.0   1.0   1.0   1.0                              Water          2.0   2.0   3.0   3.0   3.0   3.0                              Silicone Surfactant I                                                                        0.1   0.1   0.1   0.1   0.1   0.1                              Cure Temp., °F.                                                                       200                                                                              250                                                                              200                                                                              250                                                                              200                                                                              250                                                                              200                                                                              250                                                                              200                                                                              250                                                                              200                                                                              250                           Coating Properties                                                            Reverse Impact, in.-lbs.                                                                     125                                                                              5  125                                                                              5  100                                                                              15 5  25 320                                                                              320                                                                              320                                                                              5                             Acetone Rubs   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                           Pencil Hardness                                                                              2H 4H 2H 4H 2H 3H 2H F  2B 2H 3H 4H                            % Adhesion Failure                                                                           100                                                                              0  100                                                                              0  90 75 90 95 0  0  30 20                            Wet Pencil Hardness*                                                                         -- F  -- 3B -- B  -- 4B -- HB -- HB                            __________________________________________________________________________    Coating        7     8     9     10    11    12                               __________________________________________________________________________    Formulation, parts,                                                           Example 8, Run (1)                                                                           --    --    --    --    --    --                               Example 8, Run (2)                                                                           --    --    --    --    --    --                               Example 8, Run (3)                                                                           8     6     10    --    --    --                               Example 8, Run (4)                                                                           --    --    --    8     10    12                               Hexamethoxymethylmelamine                                                                    6     14    10    12    10    8                                p-Toluenesulfonic acid                                                                       1.0   1.0   1.0   1.0   1.0   1.0                              Water          3.0   3.0   3.0   3.0   3.0   3.0                              Silicone Surfactant I                                                                        0.1   0.1   0.1   0.1   0.1   0.1                              Cure Temp., °F.                                                                       200                                                                              250                                                                              200                                                                              250                                                                              200                                                                              250                                                                              200                                                                              250                                                                              200                                                                              250                                                                              200                                                                              250                           Coating Properties                                                            Reverse Impact, in.-lbs.                                                                     300                                                                              150                                                                              5  5  200                                                                              5  75 5  125                                                                              5  175                                                                              5                             Acetone Rubs   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                           Pencil Hardness                                                                              2H H  4H 5H 4H 5H 3H 5H 3H 5H 2H 4H                            % Adhesion Failure                                                                           15 100                                                                              0  0  0  0  15 2  2  5  2  95                            Wet Pencil Hardness*                                                                         -- 4B H  H  H  H  F  H  B  2H 2B H                             __________________________________________________________________________     *Wet pencil hardness was determined after immersing the samples in            50° C. water for 16 hours.                                        

EXAMPLE 9

Part A--A 160 grams portion of the ester diol ethoxylate of Part A ofExample 1 was reacted with 40 grams of IPDI for 2 hours at about 50° C.in contact with 0.2 gram of stannous octoate as catalyst to produce amixture containing unreacted ester diol ethoxylate and its hydroxylterminated diurethane derivative.

Part B--To the above reaction mixture there were added 35.3 grams ofphthalic anhydride and 58.8 grams of 2-ethoxyethyl acetate. The mixturewas heated for 30 minutes at 140° C. to produce the phthalic anhydridepartially capped reaction product mixture.

Part C--A series of coating compositions was prepared and cured by theprocedures described in Example 1. Coatings 1 to 4 were cured for 20minutes at 350° F.; coating 5 was cured at 250° F. The composition andproperties are tabulated below:

    ______________________________________                                        Coating       1       2       3     4     5                                   ______________________________________                                        Formulation, parts                                                            Example 9, Part B                                                                           8       10      12    10    10                                  Hexamethoxymethyl-                                                                          12      10      8     10    10                                  melamine                                                                      Silicone Surfactant I                                                                       0.1     0.1     0.1   0.1   0.1                                 p-Toluenesulfonic acid                                                                      0       0       0     1.25  1.25                                Ethoxyethyl Acetate                                                                         2.0     2.0     2.0   2.0   2.0                                 Coating Properties                                                            Reverse Impact, in-lbs.                                                                     300     300     300   5     15                                  Acetone Rubs  14      100     100   100   100                                 Pencil Hardness                                                                             4B      HB      HB    5H    3H                                  Adhesion, %   100     100     100   100   100                                 ______________________________________                                    

Preparation of Epoxide Modified Ester Diol Alkoxylates V and V A AndFormulations Thereof EXAMPLE 10

Part A--A 348 grams portion of the liquid ester diol ethoxolate of PartA of Example 1, 52 grams of Epoxide A and 1.2 grams of stannous octoate(added in two portions) were reacted at 150° C. for 10 hours. Theepoxide modified ester diol ethoxolate produced contained 0.68 weightpercent unreacted Epoxide A in the mixture.

Part B--A series of aqueous coating compostion was produced and curedfollowing the procedures described in Example 1. The data are summarizedin the following table:

    __________________________________________________________________________    Coating        1     2     3     4                                            __________________________________________________________________________    Formulation, parts                                                            Example 10 Part A                                                                            8.0   10.0  12.0  14.0                                         Hexamethoxymethylmelamine                                                                    12.0  10.0  8.0   6.0                                          p-Toluenesulfonic acid                                                                       1.0   1.0   1.0   1.0                                          Distilled Water                                                                              2.0   2.0   2.0   2.0                                          Silicone Surfactant I                                                                        0.1   0.1   0.1   0.1                                          Cure Temp., °F.                                                                       200                                                                              250                                                                              200                                                                              250                                                                              200                                                                              250                                                                              200                                                                              250                                       Coating Properties                                                            Reverse Impact, in-lbs.                                                                      5  <5 <5 <5 25 <5 50 25                                        Acetone Rubs   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                       Pencil Hardness                                                                              5H 5H 4H 5H 2H 5H F  H                                         __________________________________________________________________________

The results indicate that hard, thermoset coatings were prepared.

EXAMPLE 11

Part A--A mixture of 300 grams of the epoxide modified ester diolethoxalate of Part A of Example 10, 75 grams of phthalic anhydride and94 grams of 2-ethoxyethyl acetate was heated and reacted for 30 minutesat 140° C. to produce the phthalic anhydride capped derivative of theepoxide modified ester diol ethoxylate having a Brookfield viscosity of500 cps at 25° C.

Part B--A coating composition was produced by blending 12.5 grams of thecapped product of Part A above, 10 grams of hexamethoxymethylmelamine,0.1 gram of Silicone Surfactant I, and 2 grams of 2-ethoxyethyl acetate.Films prepared according to the procedure described in Example 1 werecured for 20 minutes at 350° F. The cured films obtained achieved a Bpencil hardness, 100 acetone rubs, and 320 inch-pounds of reverse impactresistance.

Preparation of Miscellaneous Fromulations Using Polyol And LatexesEXAMPLE 12

A series of coating compositions was produced using various anhydridemodified ester diol ethoxylates produced supra in conjunction with a lowmolecular weight polyol. The formulations and their coating propertiesare tabulated below; all coatings were cured for 20 minutes at 250° F.

    ______________________________________                                        Coating        1      2      3    4    5    6                                 ______________________________________                                        Formulation, parts                                                            Example 5, Part A Adduct                                                                     8.5    7.0    0    0    0    0                                 Example 6, Part A Adduct                                                                     0      0      8.5  7.0  0    0                                 Example 7, Part A Adduct                                                                     0      0      0    0    8.5  7.0                               Trimethylolpropane                                                                           1.5    3.0    1.5  3.0  1.5  3.0                               (TMP)                                                                         Hexamethoxymethyl-                                                                           10     10     10   10   10   10                                melamine                                                                      Phosphoric acid                                                                              0.2    0.2    0.2  0.2  0.2  0.2                               Silicone Surfactant I                                                                        0.1    0.1    0.1  0.1  0.1  0.1                               Ethoxyethyl Acetate                                                                          2.0    2.0    2.0  2.0  3.0  3.0                               Coating Properties                                                            Reverse Impact, in-lbs.                                                                      100    <5     25   <5   75   <5                                Acetone Rubs   100    100    100  100  100  100                               Pencil Hardness                                                                              3H     5H     3H   5H   3H   6H                                Adhesion, %    100    100    100  100  100  100                               ______________________________________                                    

All films were clear, smooth, glossy, and thermoset in character.Adhesion was excellent. The formulations containing the large amount ofTMP were very hard and as a result had minimal impact resistance.

EXAMPLE 13

Coating compositions were produced similar to those described in Example12 but containing higher concentrations of the Adducts and decreasedtrimethylolpropane concentrations. The coatings were cured at 250° F.for 20 minutes. The results are tabulated below.

    ______________________________________                                        Coating         1     2     3   4   5    6   7   8                            ______________________________________                                        Formulation, parts                                                            Example 5, Part A Adduct                                                                      9.0   9.5   0   0   0    0   0   0                            Example 6, Part A Adduct                                                                      0     0     9.0 9.5 9    9   0   0                            Example 7, Part A Adduct                                                                      0     0     0   0   0    0   9.5 9.0                          Trimethylolpropane                                                                            1.0   0.5   1.0 0.5 1.0  1.0 1.0 0.5                          Hexamethoxymethyl-                                                                            10    10    10  10  6.7  15  10  10                           melamine                                                                      Phosphoric acid 0.1   0.1   0.1 0.1 0.1  0.1 0.1 0.1                          Silicone Surfactant I                                                                         0.2   0.2   0.2 0.2 0.2  0.2 0.2 0.2                          Ethoxyethyl Acetate                                                                           2.0   2.0   2.0 2.0 2.0  2.0 2.0 2.0                          Coating Properties                                                            Reverse Impact, in-lbs.                                                                       25    50    50  25  25   25  50  75                           Acetone Rubs    ←                                                                              ←                                                                              ←                                                                            ←                                                                            100  →                                                                          →                                                                          →                     Pencil Hardness 2H    2H    2H  2H  3H   H   3H  2H                           Adhesion, %     ←                                                                              ←                                                                              ←                                                                            ←                                                                            100  →                                                                          →                                                                          →                     ______________________________________                                    

Thus good overall coating properties were obtained in all instances.Adhesion was excellent.

EXAMPLE 14

A pigmented composition was produced by mixing 90 grams of the productof Part A of Example 6, 100 grams of hexamethoxymethylmelamine, 10 gramsof the polycaprolactone triol used in Part B of Example 6, 140 grams oftitanium dioxide, and 40 grams of 2-ethoxyethyl acetate and rollingovernight in a ball mill. A 19-gram portion of the mixture was blendedwith 0.2 gram of stannous chloride and 1 gram of 2-ethoxyethyl acetateto produce a pigmented coating composition. A film was preparedaccording to the procedure described in Example 1 and cured for 20minutes at 200° F. The film produced was solvent resistant (more than100 acetone rubs), impact resistant (more than 320 inch-pounds), and hada B pencil hardness.

EXAMPLE 15

A series of coating compositions was produced by blending astyrene/ethyl acrylate/methacrylic acid/2-hydroxyethyl acrylate latexcomposition having a total solids of 43 weight percent with the productof Part A of Example 6. The aqueous latex was modified to improve itsfilm-forming properties and to establish that the anhydride modifiedester diol alkoxylates act as a reactive coalescing aid. Theformulations were produced by mixing the components described in thefollowing table at room temperature. The product of Part A of Example 6was diluted to 50 weight percent solids with distilled water andneutralized to a pH of 7.4 with N,N-dimethylethanolamine.

    ______________________________________                                        Run         1      2      3    4    5    6    7                               ______________________________________                                        Compositon, solids                                                            Latex, gms. 10     10     10   10   10   10   10                              Example 6, Part A                                                                         0      0.5    1.0  1.5  0.5  1.0  0.5                             adduct, gms.                                                                  Hexamethoxy-                                                                              0      0      0    0    0.5  0.5  1.0                             methylmelamine                                                                Water       13.3   13.8   14.3 14.8 13.8 14.3 13.8                            ______________________________________                                    

Films were cast on Bonderite No. 37 steel panels with a No. 60wire-wound rod and allowed to stand under ambient conditions overnight.The films were then observed for appearance and placed in an oven for 20minutes at 350° F. The results are reported in the following table:

    ______________________________________                                        Run        1       2      3    4    5    6    7                               ______________________________________                                        Film Properties                                                               Appearance                                                                              (1)      (1)    (2)  (3)  (4)  (3)  (3)                             prior to curing                                                               Appearance                                                                              (1)      (1)    (2)  (3)  (4)  (3)  (3)                             after cure                                                                    Acetone rubs,                                                                           No cure  60     100  100  100  100  100                             cycles                                                                        Reverse impact,                                                                         No cure  <5     15   300  <5   5    4H                              in-lbs.                                                                       Pencil hardness                                                                         No cure  F      F    2B   H    H    300                             ______________________________________                                         (1) Heavy mud cracking                                                        (2) Moderate mud cracking                                                     (3) Smooth                                                                    (4) Trace of mud cracking                                                

EXAMPLE 16

Part A--A reactor equipped with a stirrer, condenser, nitrogen inlettube and thermometer was charged with 100 parts of the ester diolpropoxylate of Experiment I and 59 parts of phthalic anhydride. Themixture was then heated to 140° C. and stirred at this temperature for90 minutes. The anhydride modified ester diol propoxylate adduct wasclear, viscous and had an acid number of 138 mgm. of KOH/gm. A 5 gramportion diluted with 15 grams of 2-ethoxyethyl acetate had a Brookfieldviscosity of 460 cps at 27° C. (No. 4 spindle, 100 rpm).

Part B--A series of catalyzed coating compositions was produced, appliedto steel panels using a No. 40 wire wound rod and cured. Theformulations contained 0.1 gram of Silicone Surfactant I and thefollowing components in grams:

    ______________________________________                                         Formulation      A       B       C     D                                     ______________________________________                                        Part A Adduct     10      10      10    10                                    Hexamethoxymethylmelamine                                                                       4.3     4.8     5.6   0                                     Epoxide A         0       0       0     10.8                                  p-Toluenesulfonic Acid                                                                          0.05    0.05    0.05  0                                     Stannous Octoate  0       0       0     0.2                                   Butyl Acetate     3.1     3.2     3.4   4.9                                   2-Ethoxyethyl Acetate                                                                           3.0     3.1     3.3   4.0                                   ______________________________________                                    

Formulations A, B and C were cured at 300° F. and D at 250° F. for 20minutes. All cured coatings had reverse and front impacts greater than320 in.-lb. and 100% crosshatch adhesion values. Formulations A, B and Cpassed 100 acetone rubs; formulation D, 65 acetone rubs. The pencilhardness values of formulations A, C and D were 2H, that of B was H.

Part C--A second series of formulations was prepared identical toFormulations A to D but without the addition of any p-toluenesulfonicacid or stannous octoate. These are identified as Formulations E, F, Gand H respectively. In addition Formulation I was produced containing 10parts of the Part A Adduct, 0.1 part of Silicone Surfactant I, 7 partsof butyl acetate, 6.3 parts of 2-ethoxyethyl acetate and 21 parts ofbis(3,4-epoxycyclohexylmethyl) adipate. The formulations were applied tosteel panels as in Part B and cured at 300° F. for 20 minutes.(Formulations H and I were also given an initial precure of 20 minutesat 250° F.). All cured coatings had reverse and front impacts greaterthan 320 in.-lb. and 100% crosshatch adhesion values. Formulations G, Hand I passed 100 acetone rubs; formulation E, 50 acetone rubs;formulation F, 75 acetone rubs. The pencil hardness values of F, G and Iwere F, that of E was H and that of H was 3H.

EXAMPLE 17

A pigment grind was prepared using 100 parts of the anhydride modifiedester diol ethoxylate of Example 1, Part B, 180 parts of titaniumdioxide, 2 parts of stannous octanoate, 1 part of Silicone Surfactant I,and 4 parts of xylene by grinding in a ball mill.

To 161.5 parts of the pigment grind there were added 28.9 parts ofbis(3,4-epoxycyclohexylmethyl) adipate, 20.35 parts of4,4'-dicyclohexylmethane diisocyanate and 40 parts of xylene and themixture thoroughly blended to yield a formulation having a viscosity of180 cps at room temperature. Steel panels were spray-coated and cured at220° F. and 250° F. to yield hard, adherent, thermoset coatings withgood impact resistance and high gloss.

EXAMPLE 18

A series of coating formulations was produced containing the indicatedcomponents. They were then applied to steel panels using a No. 40wire-wound rod and cured at 220° F. and 250° F. for 20 minutes to yieldhard, adherent, thermoset coatings with generally excellent impactresistance. Each formulation contained 10 parts of the anhydridemodified ester diol ethoxylate of Example 1, Part B, 0.2 part ofstannous octanoate, 0.1 part of Silicone Surfactant I and 2 parts of2-ethoxyethyl acetate in addition to the epoxides identified below.

    ______________________________________                                                    Epoxide      Isocyanate                                           Formulation   A        B         A                                            ______________________________________                                        (a)           3.74     0         4.07                                         (b)           0        5.78      4.07                                         (c)           7.54     0         0.5                                          (d)           0        11.55     0.5                                          (e)           11.34    0         0.5                                          (f)           0        17.3      0.5                                          ______________________________________                                         Epoxide B=bis(3,4epoxycyclohexyl-methyl)adipate                               Isocyanate A=4,4dicyclohexylmethane diisocyanate                         

EXAMPLE 19

A formulation was produced by blending 10 parts of the anhydridemodified ester diol ethoxylate of Example 1, Part B, 5.78 parts ofbis(3,4-epoxycyclohexyl-methyl) adipate, 4.07 parts of4,4'-dicyclohexylmethane diisocyanate and 0.2 part of stannousoctanoate. One mil coatings were applied to a 0.5 inch by 1 inch portionof two 1 inch wide by 1.5 inches long metal strips. The two coated edgeswere held together with a paper clip and cured for 20 minutes at 300° F.In two replicate tests, it was found that an average tensile forceapplied to the two ends of the adhered strips of about 600 pounds wasrequired to break the adhesive bond that had been formed.

EXAMPLE 20

A series of adhesive compositions was prepared, each containing 10 partsof the anhydride modified ester diol ethoxylate of Example 1, Part B,and the following components:

    ______________________________________                                        Adhesive              (1)      (2)                                            ______________________________________                                        Epoxide A             0        10                                             Hexamethoxymethylmelamine                                                                           10       0                                              Stannous octoate      0        0.2                                            p-Toluenesulfonic Acid                                                                              0.2      0                                              ______________________________________                                    

Adhesive (1) required an average tensile force of 8.8 pounds to breakthe bond; an average tensile force of 37.5 was required with Adhesive(2).

What is claimed is:
 1. A high solids composition comprising a blend ofan aqueous acrylic latex of from about 5 to about 50 weight percent,based on the total solids content of said latex, of an anhydridemodified ester diol alkoxylate comprising the reaction product of (A) anester diol alkoxylate of the general formula: ##STR15## wherein m is aninteger having a value of from 2 to 4, n is an integer having a value offrom 1 to 5, x and y are integers each having a value of from 1 to 20and R is an alkyl group having from 1 to 8 carbon atoms; and (B) anintramolecular anhydride of a polycarboxylic acid.
 2. A high solidscomposition comprising a blend of an aqueous acrylic latex and fromabout 5 to about 50 weight percent, based on the total solids content ofsaid latex, of an isocyanate modified ester diol alkoxylate comprisingthe reaction product of (A) an ester diol alkoxylate of the generalformula: ##STR16## wherein m is an integer having a value of from 2 to4, n is an integer having a value of from 1 to 5, x and y are integerseach having a value of from 1 to 20 and R is an alkyl group having from1 to 8 carbon atoms; and (B) from 0.025 to 0.9 isocyanato equivalent perhydroxyl equivalent of a polyisocyanate.
 3. A high solids compositioncomprising a blend of aqueous acrylic latex and from about 5 to about 50weight percent, based on the total solids content of said latex, of ananhydride capped isocyanate modified ester diol alkoxylate comprisingthe reaction product of (A) an ester diol alkoxylate of the generalformula: ##STR17## wherein m is an integer having a value of from 2 to4, n is an integer having a value of from 1 to 5, x and y are integerseach having a value of from 1 to 20 and R is an alkyl group having from1 to 8 carbon atoms; and (B) from 0.025 to 0.9 isocyanato equivalent perhydroxyl equivalent of a polyisocyanate capped with from 0.1 to 1anhydride equivalent per hydroxyl equivalent initially charged with anintramolecular anhydride of a polycarboxylic acid.
 4. A high solidscomposition comprising a blend of an aqueous acrylic latex and fromabout 5 to about 50 weight percent, based on the total solids content ofsaid latex, of an epoxide modified ester diol alkoxylate comprising thereaction product of (A) an ester diol alkoxylate of the general formula:##STR18## wherein m is an integer having a value of from 2 to 4, n is aninteger having a value of from 1 to 5, x and y are integers each havinga value of from 1 to 20 and R is an alkyl group having from 1 to 8carbon atoms; and (B) from 0.2 to 1 mole of a diepoxide per mole of (A).5. A high solids composition comprising a blend of an aqueous acryliclatex and from about 5 to about 50 weight percent, based on the totalsolids content of said latex, of an anhydride capped epoxide modifiedester diol alkoxylate comprising the reaction product of (A) an esterdiol alkoxylate of the general formula: ##STR19## wherein m is aninteger having a value of from 2 to 4, n is an integer having a value offrom 1 to 5, x and y are integers each having a value of from 1 to 20and R is an alkyl group having from 1 to 8 carbon atoms; and (B) from0.2 to 1 mole of a diepoxide per mole of (A) capped with from 0.1 to 1anhydride equivalent per hydroxyl equivalent initially charged with anintramolecular anhydride of a polycarboxylic acid.
 6. A high solidscomposition as claimed in claim 1, wherein a polycaprolactone polyol isadditionally present.